Organo antimony mercaptides and the preparation thereof



United States Patent Office Patented Sept. 22, 1970 3,530,158 ORGANOANTIMONY MERCAPTIDES AND THE PREPARATION THEREOF John R. Leebrick, OldLyme, Conn., and Nathaniel L.

Remes, Livingston, N.J., assignors to M & T Chemicals Inc., New York,N.Y., a corporation of Delaware No Drawing. Application Apr. 24, 1964,Ser. No. 362,483, which is a continuation-in-part of application Ser.No. 241,023, Nov. 29, 1962. Divided and this application Nov. 25, 1966,Ser. No. 612,063

Int. Cl. C07f 9/90 US. Cl. 260-446 26 Claims ABSTRACT OF THE DISCLOSURENovel compositions are provided having fungicidal and bacteriocidalproperties and having the general formula R SbX wherein R is selectedfrom the group consisting of alkyl, alkenyl, alkynyl, aryl, cycloalkyl,and cycloalkenyl, X is selected from the group consisting of halide,carboxylate, alkoxide, oxide, hydroxide, sulfide, mercaptide, and n isan integer less than 4.

This application is a division of Ser. No. 362,483, filed Apr. 24, 1964,and now abandoned, which divisional is a continuation-in-part of Ser.No. 241,023, filed Nov. 29, 1962, and now abandoned.

This invention relates to methods of preventing and inhibiting thegrowth of microorganisms such as bacteria and fungi and to compositionsof matter utilized in these methods. The invention also relates tomaterials which have been made resistant to attack by microorganismssuch as bacteria and fungi by the aforesaid methods.

It is an object of this invention to provide methods for inhibiting andpreventing the growth of microorganisms. It is still another object ofthe invention to provide bacteria-resistant compositions includingpaints, plastics, and fibrous products such as textiles and paperproducts. It is also an object of this invention to provide sanitizercompositions having particular utility in hospital treatment. Otherobjects will be apparent to those skilled in the art on inspection ofthe following description.

In accordance with certain of its aspects, the method of this inventionfor protecting a medium susceptible to attack by microorganismscomprises applying to the locus to be protected an effective amount of RSbX wherein R is selected from the group consisting of alkyl, alkenyl,alkynyl, aryl, cycloalkyl, and cycloalkenyl, X is selected from thegroup consisting of halide, carboxylate, alkoxide, oxide, hydroxide,sulfide, mercaptide, and n is an integer less than 4.

In the compounds R SbX which may be used in practice of this invention,R may be alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, or arylincluding such groups when inertly substituted. When R is alkyl, it mayinclude methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, n-amyl,n-octyl, Z-ethylhexyl, etc. as well as substituted alkyls includingphenylethyl, benzyl, etc. Typical alkenyl groups which may be employedmay include vinyl, 2-propeny1 (i.e. allyl), l-propenyl, l-butenyl,2-butenyl, etc. as well as inertly substituted alkenyl groups typifiedby 4-phenyl, buten-l-yl, etc. Typical cycloalkyl groups may includecyclohexyl, cycloheptyl, cyclooctyl as well as inertly substitutedcycloalkyl groups including 2-methyl cycloheptyl, S-butyl cyclohexyl,3-methylcyclohexyl, etc. Typical alkynyl groups which may be employedinclude propyn-l-yl, propyn-2-yl, butyn-l-yl, phenylethynyl, ethynyl,etc. Typical aryl groups which may be employed may include phenyl,tolyl, xylyl, chlorophenyl, dimethylaminophenyl, etc. Where several Rgroups may be present, they may be the same or different.

In the compound R SbX 11 may be an integer less than 4 Le. n may be 1,2, or 3. When n is 1, the compound may be RSbX when n is 2, the compoundmay be R SbX; when n is 3, the compound may be R Sb. It will be apparentto those skilled in the art that when X is a divalent group ashereinafter set forth, the compound may be R Sb-X SbR or alternativelyRS-bX.

The X group in the compound R SbX may be halide, sulfide, oxide,carboxylate, phenoxide, alkoxide, and mercaptide. Typical halides may bechloride, bromide, etc. Typical carboxylates may be acetate, laurate,benzoate, salicylate, butyrate, propionate, etc. Typical phenoxides mayinclude phenoxide se, o-phenylphenoxide, S-quinolyloxide,pentachlorophenoxide, p-methylphenoxide, etc. Typical alkoxides mayinclude methoxide, ethoxide, n-propoxide, i-propoxide, n-butoxide, etc.Typical mercaptides include phenyl mercaptide, lauryl mercaptide, butylmercaptide, etc. It will be apparent when X is divalent, e.g. sulfide oroxide, the formula may become e.g. R,,Sb---OSbR in which case It may be2.. If desired, the X groups or the R groups may be cyclized eg.cyclopentamethylene antimony chloride or phenylantimony maleate. Whereseveral X groups are present, they may be the same or different.

, Typical specific compounds which may be employed when n is 1 mayinclude methyl antimony dichloride, ethyl antimony dibromide, n-propylantimony diacetate, n-propyl antimony dimethoxide, n-butyl antimonydichloride, n-butyl antimony dibromide, n-butyl antimony diacetate,n-butyl antimony dilaurate, n-butyl antimony dimethoxide, n-butylantimony oxide, n-butyl antimony dilaurylmercaptide, n-butyl antimonysulfide, i-butyl antimony dichloride, i-butyl antimony diacetate,cyclohexyl antimony dichloride, cyclopentyl antimony diacetate, n-octylantimony dibromide, vinyl antimony diacetate, allyl antimony dibenzoate,cyclohexenyl antimony dilau rate, butyn-l-yl antimony dichloride,phenylethynyl antimony diacetate, phenyl antimony dichloride, tolylantimony dibromide, p-chlorophenyl antimony sulfide.

Typical specific compounds which may be employed when n is 2 may includedimethyl antimony chloride, diethyl antimony acetate, di-n-propylantimony laurate, dii-propyl antimony methoxide, di-n-butyl antimonybromide, di-n-butyl antimony methoxide, bis(di-n-butyl anti mony) oxide,dicyclohexyl antimony chloride, diallyl antimony bromide, dibutyn-l-ylantimony acetate, diphenyl antimony chloride.

Typical specific compounds which may be employed when n is 3 may includetrimethyl antimony, triethyl antimony, tripropyl antimony, tri-n-butylantimony, tri-ibutyl antimony, tri-n-amyl antimony, tri-n-octylantimony, tri-p-chlorophenyl antimony, tri-p-tolyl antimony, triphenylantimony, tricyclohexyl antimony, triallyl antimony, tri(phenylethynyl)antimony.

The most highly preferred compounds may be RSbXz, typically phenylantimony dichloride, phenyl antimony diacetate, and n-butyl antimonydichloride. The preferred compounds which may be employed in practice ofthis invention, may also include tri-n-butyl antimony, triphenylantimony, trivinyl antimony, tri-n-propyl antimony, di-butyl antimonychloride, diphenyl antimony chloride, diphenyl antimony acetate, etc.

These compounds may be generally available or may be readily made in thelaboratory. For example, compounds R Sb, typically triphenyl antimony,may be made by the reaction of the Grignard reagent RMgHal with SbHalwherein Hal is halide, usually chloride. Reaction of R Sb with SbHalproduces R SbHaI and RSbHal which may be separated. R SbHal or RSbHalmay be reacted with e.g. sodium sulfide to produce R Sb-S-SbR Or RSbS;with ammonium hydroxide to produce R SbOH or RSbO; with sodium ethoxideto produce R Sb(ethoxide) or RSb(ethoxide) with sodium mercaptide, e.g.sodium lauryl mercaptide to produce R Sb lauryl mercaptide or RSb(1aurylmercaptide) R SbHa1 may be reacted with ammonium carboxylate, e.g.ammonium acetate or ammonium butyrate, to produce R Sb(carboxylate).RSbO may be reacted with carboxylic acid, e.g. acetic acid, to produceRSb(carboxy1ate) e.g. RSb(acetate) It is a particular feature of thisinvention that antimony compounds R SbX may be used to control a widerange of microorganisms including bacteria and fungi. The compounds ofthis invention are highly effective against a wide spectrum of bacteriaincluding Gramnegative and Gram-positive bacteria. Typical Gram-positivebacteria against which the technique of this invention may beparticularly effective may include Staph. aurezzs.

4 Typical Gram-negative bacteria which may be controlled in accordancewith certain aspects of this invention may include A. aerogenes and P.aeruginosa. It is a particular feature of this invention that inaccordance with certain aspects it may be used to control C. albicans,A. flavus, and P. funiculosum.

In practice of this invention, these microorganisms and preferablybacteria may be controlled in a wide variety of loci. It is possibleaccording to this invention to treat plastics, textiles, paper products,paints and other specific materials which may serve as media in whichmicroorganisms may grow. Plastics, textiles, paper products and paintsare illustrative of the materials which are rendered resistant to attackwhen treated by applying the antimony compound to the surface and/or byincorporation therein. The plastics is massive and in fiber form mayinclude urethanes, halogenated polymers and eopolymers such as polyvinylchloride and polyvinyl chloride-acetate copolymers, polyesters,polyamides, polyolefins, and natural rubbers, synthetic rubbers, etc.Natural fiber products that may be protected include paper products,hemp, and felts. Paints may be protected in the can and also afterapplication. Typical paints may include interior and exterior vinyllatex and alkyd paints, non-synthetic fiat natural paints, the acrylics,and the vinyl, and ani-fouling paints such as the acrylic and the vinylvarieties thereof. The antimony compounds are also useful in preservingadhesives; in secondary oil recovery processes; in paper mill slimecontrol processes; and in methods or controlling Staph. aureus inhospitals. They may be a useful and active component of detergentsanitizers and may be used for this and other purposes in the form of anaerosol material. They may also be used to protect plants and othergrowth against microorganisms (including fungi) attack. The use of thenovel bactericides of this invention to render plastics, especiallypolyvinyl chloride, resistant to attack by microorganisms and the novelresistant compositions produced thereby represent preferred embodimentsof this invention.

Practice of this invention may be illustrated by ref- 4 31, 16, 8, 4,and 2 parts per million (ppm). Each broth was inoculated with the testorganism and the broth incubated at 37 C. for two days. The organismgrowth was visually observed. The broth containing the minimumconcentration which caused complete inhibition of the growth of theorganism is listed.

From Table I, it will be apparent that the noted compounds may beemployed in unexpectedly low levels to kill both Gram-negative andGram-positive bacteria. As will be apparent to those skilled in the art,these compounds are unexpectedly highly effective.

In Table II, there are listed the results of a standard Broth DilutionTest against certain fungi.

TABLE II C. A. P. funic- Coinpound albz'cans flavus ulosum Diphcnylantimony chloride 63 63 500 Phenyl antimony dichloride. 63 250 250Tributyl antimony 63 250 125 From Table II, it will be apparent to thoseskilled in the art that the compounds of this invention unexpectedlyexhibit a high order of activity against fungi.

The activity of the noted compounds in practice of this invention mayalso be demonstrated by the standard Agar Diffusion Test (Filter PeterDisc Method) as set forth in Table II. In this standard test, compoundswere diluted in acetone to obtain the following stock solutions: 5, 2.5,1.25, 0.63, 0.31%. Filter paper discs, 10 mm. in diameter, were dippedin the test solution and the solvent then allowed to evaporate. AATCCBacteriostasis agar, held at C., was inoculated to 1% with an 1824 hournutrient broth culture of S. aureus. The seeded agar was distributed atthe rate of 15 ml./ 10 cm. Petri dish and allowed to solidify. Thetreated filter paper discs were placed on the seeded agar. Then theplates were incubated at 37 C. for 48 hours. Inhibition was determinedby a zone or halo adjacent to the treated disc.

It will be apparent from inspection of Table III that the compounds ofthis invention, typified by triphenyl antimony, unexpectedly perform asbacteriostats as judged by this test.

Table IV infra shows the results of certain compounds erence to thefollowing wherein various compounds were in the Bulk Agar DiffusionTest.

TABLE IV E. Compound S. aureus coli A. flaws mycoz'rlcs Diphenylantimony chloride, mm 16 16 Ihenyl antimony dichloride, mm 23 22Triphonyl antimony, mm 4 3 tested against a wide range ofmicroorganisms. In Table I there is disclosed the results of thestandard Broth Dilution Test wherein various compounds as noted weretested against bacteria.

In the tables showing Broth Dilution Test results, the tests arereported showing the activity of the compounds against notedmicroorganisms. In each example. a series of tests were carried out whenthe compound was placed within a nutrient broth in amount of 500, 250,125, 63,

It will be apparent from Table IV that the noted compounds may beunexpectedly active against bacteria and fungi. (The blank spaces in thetable represent tests which were not performed in this series.)

In another series of comparative standard Agar Diffusion Tests, selectedcompounds were blended into polyvinyl chloride formulations containingparts by weight of Geon 101EP brand of polyvinyl chloride, 50 parts ofdioctyl phthalate, 0.25 part of stearic acid, and

2 parts of a standard stabilizer for polyvinyl chloride againstdeterioration by heat and light. Typical formulations and results oftests are shown in Table V.

1 Parts of compound per 100 parts of resin.

It will be apparent to those skilled in the art that the notedcompositions are unexpectedly superior in their activity against thenoted organisms.

It is a particular feature of this invention that the preferredformulations prepared in accordance therewith possess an unexpectedlyhigh activity against Gramnegative bacteria. It will be obvious to thoseskilled in the art that prior art bacteriocides possess little or noactivity against Gram-negative bacteria when used in concentrations atwhich the preferred formulations of this invention (e.g. thosecontaining phenyl antimony dichloride) may control a wide range ofbiocidal targets including Gram-negative bacteria. For example, in acomparison by means of a Broth Dilution Test against phenyl mercuryacetate (a typical prior art bacteriocide), it was found that phenylantimony dichloride was twice as active as phenyl mercury acetateagainst A. aerogenes and P. aeruginosa.

The method of this invention may be effected by using the noted compoundR SBX in solid, liquid, or gaseous (including spray) formulations. Itmay for example be carried out by applying the compound to the surfaceof the material to be protected and/or admix ing the compound with thematerial to be protected during the fabrication of said material. Thecompounds may be used per se, particularly when they are incorporatedinto the material during the preparation or fabrication. Many materials,particularly fibrous products such as textiles, may be treated byapplying the compound to the surface by dipping, padding, spraying, etc.They may be used in the form of a bactericidal composition in which thecompound is the active component or one of the active components. Liquidcompositions may be utilized in which the compound is dissolved and/orsuspended in a solvent. Solid compositions may be utilized in which thecompound is mixed with a carrier or diluent. The carrier may be inert,such as talcs, clays, diatomaceous earth, flours, etc., or it may haveactivity such as that shown by the quaternary ammonium compounds. Theliquid formulations of the emulsion type will often include a dispersionagent as the anionic, cationic, or nonionic surface agents. To obtainfungicidal and/or bactericidal compositions having an extremely broadspectrum of activity, the compound may be formulated with other activematerials such as the triorganotins, pentachlorophenol,copper-8quinolinolate, bisphenols, ophenylphenol, and polybrominatedsalicylanilides.

It will be apparent to those skilled in the art that the containedamount of the active compound R SBX present in the total composition maybe sufiicient to provide an effective amount at the locus to beprotected against the appropriate microorganism. Typically suchcontained amounts may range from very low concentrations typically0.00l%0.002% up to 90%-l00%. These concentrations will permit attainmenton the medium susceptible to attack at the locus to be protected, ofeffective amounts which may for example be, in Water treatment, 1-100ppm. or in plastic treatment, 50-2000 p.p.m., etc.

Illustrative of the compositions containing the active antimony compoundare those of Examples 14.

EXAMPLE 1 Spray composition: Parts by weight Phenyl antimony dichloride0.02 Toluene 15 Fluorohydrocar bon gaseous propellant 84.98

EXAMPLE 2 Liquid composition:

Phenyl anitmony dichloride 1 Acetone 20 Toluene 79 EXAMPLE 3 Emulsioncomposition:

Diphenyl antimony acetate 0.02 Toluene l5 Non-ionic surfactants (TritonX100 brand of isooctyl phenoxy polyethoxy ethanol)" 20 Water 64.98

EXAMPLE 4 Solid composition:

Diatomaceous earth Triphenyl antimony 20 Specific formulations which maybe used in practice of this invention may include those set forth inExamples 5-7.

EXAMPLE 5 Acrylic anti-fouling paint: Parts by Weight Titanium dioxide160 Aluminum silicate 48 Talc 12 Methyl methacrylate-butyl methacrylatecopolymer (40% in thinner) 433 Mineral spirits 148 Dibutyl antimonyacetate 50 EXAMPLE 6 Vinyl anti-fouling paint:

Titanium dioxide 150 Bentonite 14 Tricresyl phosphite 10 Vinylchloride-vinyl acetate copolymer resin 102 Toluene 223 Methyl isobutylketone 295 Phenyl antimony dichloride 35 Butyl antimony dichloride 35EXAMPLE 7 Flat interior paint:

Titanium-calcium pigment 625 Calcium carbonate Magnesium silicate 25Ester gum solution (60% non-volatile in mineral spirits) 30 Bodiedlinseel oil 200 Mineral spirits 167 Cobalt naphthenate (6% Co) 1 Leadnaphthenate (24% Pb) 2 Phenyl antimony dilaurylmercaptide 6 It is aparticular feature of certain compositions prepared in accordance withthis invention that they retain their unexpectedly high level ofbacteriocidal activity under adverse conditions. These compositions areparticularly characterized by their high activity in the presence of awide variety of surface active agents e.g. soaps, dispersants,detergents, etc. It is particularly unexpected that this activity may beretained in the presence of anionic soaps such as sodium stearate e.g.Ivory soap.

7 In an illustrative comparative test, a typical compound (phenylantimony dichloride) was tested, alone and in combination with anon-ionic detergent and with an anionic detergent such as sodiumstearate (Ivory soap), by the standard Broth Dilution Test against S.aureus and E. coli. The results may be observed from Table VII.

TABLE VII S. aureus E. 0012' Ivory soap 10 10 Non-ionic soap (TritonX-lOO brand of isooctyl phcuoxy polycthoxy ethanol) 1t) 10 Control 10 10From this table it will be apparent that the presence of an anionic soap(i.e. Ivory soap) or a non-ionic soap does not interfere with theunexpectedly superior performance of the compounds of this invention.

In order to demonstrate the effectivity of the process of this inventionto control bacteria including fungi in paper pulp, a simulated standardpaper pulp was formulated containing 8.4 parts of Whatmans No. 2 Gradefilter paper, 2.6 parts of sodium nitrate, 1 part of pearl fillercalcium sulfate, 6.5 parts of maltose, 1 part of nutrient broth BBL madeby Baltimore Biological Laboratories, 10 parts of 2% Mersize RM7OR brandof sizing material, 2.5 parts of 2% solution ofalum, and 990 parts ofwater. To this mixture there was added various concentrations (TableVIII) of phenyl antimony dichloride and (Table IX) diphenyl antimonychloride. In the several experiments, the concentrations of thesematerials were maintained at p.p.m. (control) 5, 1O, 50, 100 and 500p.p.m. The control sample was tested at 0 time to determine its contentof A. aerogenes and P. a'eruginosa. The simulated paper pulp was testedafter 24 hours to determine the content of these bacteria. The resultsare shown tabulated in Table VIII and Table IX.

TABLE VIII.PHENYL ANTIMONY DICHLORIDE Concentration, p.p.m. A. aerorcnes P. aerugi'lmsa TABLE IX.DIPHENYL ANTIMONY CHLORIDE Concentration,p.p.m. A. aerogenes P. aeruginosa 0 (control) at 0 hours 12x10 50 10 0(control) at 24 hours 18x10 20 10 5 at 24 hours 55x10 10 l0 10 at 24hours x10 10x10 at 24 hours 10x10 ll l0 at 24 hours 0 22x10 500 at 24hours 0 From inspection of the above tables, it will be apparent thatuse of the noted compounds, used in practice of this invention, permitsattainment of paper pulp characterized by its freedom from bacterialgrowth which commonly produces slime. It will be apparent for examplefrom Table VIII that phenyl antimony dichloride in concentration of aslow as 5 p.p.m. may permit substantial reduction of the bacterialcontent and use of only 100 p.p.m. will completely kill both A.aerogenes and P. aeruginosa.

The potent biocides having the formula R,,SbX wherein n is 2; R isselected from the group consisting of alkyl, alkenyl, alkynyl, aryl,cycloalkyl, and cycloalkenyl; and X is mercaptide are new compoundswhich possess valuable properties. For example, compounds of this typeare especially effective biocides for use in plastics, typicallypoly(vinyl chloride).

The compounds may have the formula R SbX 3 wherein n is 2 and X ismercaptide. Preferably, they may have the formula R SbSR wherein R is asdefined supra and R is selected from the same group as is R, i.e. R. andR are independently selected from the group consisting of alkyl,alkenyl, alkynyl, aryl, cycloalkyl, and cycloalkenyl.

When R is alkyl, it may include methyl, ethyl, n-propyl, i-propyl,n-butyl, i-butyl, n-amyl, n-octyl, 2-ethylhexyl, etc. as well as inertlysubstituted alkyls including phenylethyl, benzyl, carboethoxymethyl,etc.

Typical alkenyl groups which may be employed may include 2-propenyl(i.e. allyl), 3-butenyl, etc. as well as inertly substituted alkenylgroups typified by 4-phenyl-3- butenyl, 2-methyl-2-propenyl, etc.Typical cycloalkyl groups may include cyclohexyl, cycloheptyl,cyclooctyl as well as inertly substituted cycloalkyl groups including 2-methylcycloheptyl, 3-butylcyclohexyl, 3-methylcyclohexyl, etc. Typicalaryl groups which may be employed may include phenyl, tolyl, xylyl,chlorophenyl, dimethylaminophenyl, etc.

The novel biocides having the formula R SbX wherein n is 2 and X ismercaptide may be prepared by the reaction of R SbCl, wherein R is asdefined supra, with an alkali metal mercaptide, e.g. sodium laurylmercaptide; by the reaction of (R Sb) O with a mercaptan, e.g. phenylmercaptan, butyl mercaptan, etc. For example, diphenyl antimony chloridemay be reacted with an alkali metal mercaptide such as sodium laurylmercaptide, sodium phenyl mercaptide, sodium butyl mercaptide, sodiumethyl mercaptide, sodium n-propyl mercaptide, sodium isopropylmercaptide, sodium n-butyl mercaptide, sodium isobutyl mercaptide,sodium sec-butyl mercaptide, etc.

Preferably, the reaction may be carried out by mixing together the RSbCI and the sodium mercaptide in equimolar quantities in the presenceof an inert hydrocarbon diluent, say benzene, and heating the so-formedreaction mixture to reflux for a period of time sufiicient to completethe reaction, typically 0.5-20 hours, say 4-6 hours. By-product sodiumchloride may be filtered off and the solvent, typically benzene, may bestripped from the product.

The novel compounds may also be prepared by the reaction of (R Sb) Owith a mercaptan. For example, bis(diphenyl antimony) oxide may bereacted with ethyl mercaptan, n-propyl mercaptan, sec-butyl mercaptan,phenyl mercaptan, benzyl mercaptan, cyclohexyl mercaptan, laurylmercaptan, p-tolyl mercaptan, allyl mercaptan, etc. Reaction of (R Sb) Owith a mercaptan may preferably be effected by mixing together 1 mole ofthe former with 2 moles of the latter in the presence of an inerthydrocarbon diluent, typically benzene, and refluxing the so-formedreaction mixture for about 0.310, say 1-2 hours with a Dean-Stark trapto remove by-product water. When no further reaction is observed, theremaining solvent may be stripped otf to leave the product.

Illustrative examples of the novel products of this invention having theformula R SbX wherein n is 2; R is selected from the group consisting ofalkyl, alkenyl, alkynyl, aryl, cycloalkyl, and cycloalkenyl; and X ismercaptide may include:

di-n-butyl antimony lauryl mercaptide diphenyl antimony laurylmercaptide ditolyl antimony n-amyl mercaptide dibenzyl antimony benzylmercaptide diallyl antimony cyclohexyl mercaptide diphenyl antimonyallylmercaptide dicyclohexyl antimony n-hexyl mercaptide ditolylantimony phenyl mercaptide di-isopropyl antimony Z-ethylhexyl mercaptidedi-p-chlorophenyl antimony n-butyl mercaptide diphenyl antimony ethylmercaptoacetate.

9 EXAMPLE 8 A solution of 56.8 grams (0.1 mole) of bis(diphenylstibine)oxide and 20.8 grams (0.2 mole) of pentanethiol in 400 ml. of benzenewas heated under reflux in a flask equipped with Dean-Stark trap andreflux condenser. Within 1.5 hours, 1.8 ml. of water (100% yield) hadcollected in the top. The solvent was removed at 65 C./ 80 mm., leavinga hazy liquid which was clarified by filtration (71.0 grams; 93.7%).

The product distilled at 218 =C./0.5 mm. without apparent decomposition.

Analysis.--Calcd. for C H SSb (percent): Sb, 32.11; S, 8.46. Found(percent): Sb, 31.6; S, 7.9.

EXAMPLE 9 Diphenylantimony carboethoxymethyl mercaptide SbSCH COOC H Asolution of 56.8 grams (0.1 mole) of bis(diphenylstibine) oxide and 24grams (0.2 mole) of ethyl mercaptoacetate in 400 ml. of benzene wereheated under reflux in a flask equipped with Dean-Stark trap and refluxcondenser. Over a period of 1 hour, 1.8 ml. (100%) of water collected inthe trap. The solvent was removed by distillation at 65 C./8O mm.,leaving a yellow hazy oil which was clarified by filtration (78.0 grams;98%). This distilled at 210222 C./ 0.55 mm., with slight decomposition.

Analysis. Calcd. for C H SO Sb (percent): Sb, 30.82; S, 8.11. Found(percent): Sb, 28.6; S, 6.8

EXAMPLE 10 Di-n-butyl antimony lauryl mercaptide (C H SbSC H (C HSbCl+NaSC H (C H SbSC H +NaCl 27.2 grams (0.1 mole) of di-n-butylantimony chloride may be dissolved in 500 ml. of dry benzene and 22.5grams (0.1 mole) of sodium lauryl mercaptide added thereto. The mixturemay be heated to reflux and refluxed with stirring for 5 hours, therebyforming di-n-butyl antimony lauryl mercaptide and sodium chloride. Themixture may be filtered hot to remove sodium chloride, and the filtratestripped under vacuum to give product. If desired, the di-n-butylantimony lauryl mercaptide may be further purified by fractionaldistillation at about 0.5 mm. pressure.

The novel compounds of the formula R SbX wherein R is selected from thegroup consisting of alkyl, alkenyl, alkynyl, aryl, cycloalkyl, andcycloalkenyl; n is an integer less than 3, i.e. 1 and 2; and X isalkoxide are also new compounds which have not heretofore been known andwhich are characterized by their surprisingly high activity againstpestiferous organisms.

These novel compounds may have the formula wherein R is as describedsupra; n is an integer less than 3, i.e. 1 and 2; and X is alkoxide.More specifically, the novel compounds ma have the formula R,,Sb(OR)wherein R is as described supra; 11 is an integer less than 3; and R isalkyl, including inertly substituted alkyl and cycloalkyl.

R" may be alkyl, including methyl, ethyl, n-propyl,-

the reaction of organoantimony halide, say R SbCl with an alkali metalalkoxide or by reaction or oganoantimony halide, say R SbCl withalcohol, say R"OH, in the presence of a proton acceptor, preferablyammonia. A typical reaction may be represented as where R is thepreferred phenyl radical and n is 2, the reaction may be Examples ofalcohols R"OH which may be employed in the preferred method ofpreparation include methanol, ethyl alcohol, n-propyl alcohol, isopropylalcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol,tert-butyl alcohol, amyl alcohol, hexyl alcohol, octy alcohol, decylalcohol, dodecyl alcohol, tetradecanol, cetyl alcohol, octadecanol,2-ethylhexanol, benzyl alcohol, phenylethyl alcohol, 4-phenylbutanol,ethoxyethanol. Other equivalent compounds may also be employed.

Preferably, reaction of R SbCl and ROH may be carried out in thepresence of inert organic solvent such as benzene, toluene, hexane,heptane, etc. Stoichiometric quantities of the two reactants may be usedor an excess, or one reactant typically R"OH, may be employed. The tworeactants may be mixed together in the presence of the base, typicallyammonia, or the base and R SbCl may be mixed together prior to theaddition of ROH. When this procedure is followed, a complex between thebase and R SbCl may be formed.

When all of the reactants are present, the reaction mixture may beheated, typically to about 40-120" C., preferably -100" C. for about1-10 hours during which time the desired product may be formed, togetherwith byproduct, typically ammonium chloride. The product may be isolatedby filtering ofl by-product and distilling off any residual ROH andinert organic solvent.

Illustrative novel compounds of this invention having the formula R SbX,wherein R is selected from the group consisting of alkyl, alkenyl,alkynyl, aryl, cycloalkyl, and cycloalkenyl; n. is an integer less than3; and X is alkoxide, include:

diphenyl antimony butoxide diphenyl antimony ethoxide diphenyl antimonyn-propoxide diphenyl antimony phenylethoxide diphenyl antimonybenzyloxide phenyl antimony dibutoxide phenyl antimony diethoxide phenylantimony di-2ethylhexoxide phenyl antimony diphenylethoxide phenylantimony dibenzyloxide di-n-butyl antimony ethoxide ditolyl antimonycyclohexoxide dibenzyl antimony n-propoxide diallyl antimony butoxidedicyclohexyl antimony methoxide di-isopropyl antimony ethoxidedi-p-chlorophenyl antimony butoxide n-butyl antimony dimethoxide tolylantimony di-2-ethylhexoxide benzyl antimony diethoxide allyl antimonydibutoxide cyclohexyl antimony dimethoxide isopropyl antimony butoxidep-chlorophenyl antimony dihexoxide.

These novel compounds may be prepared by employing the desired alcoholand antimony halide in the process hereinbefore described. For example,grams (0.29 mole) of diphenyl antimony chloride may be dissolved in 2liters of anhydrous benzene and filtered clear into a 5-liter flaskunder a nitrogen atmosphere. Ammonia gas may be bubbled into thesolution over a period of 4.5

hours, during which time a white diphenylantimony chloride-ammoniacomplex precipitates. Anhydrous n-butanol, 400 ml. (0.29 mole+50%excess) may be added over a period of 15 minutes, and the resultantopaque white reaction mass heated to reflux and refluxed with stirringfor 7.5 hours. The reaction mass may then be cooled, and filtered toremove ammonium chloride. Solvent is stripped from the filtrate undervacuum to a pot temperature of 100 C./2.3 mm. Hg. The oil residue of89.4 grams (88.5% yield) which crystallizes on standing may have aboiling point of 133-141 C. at 0.5 mm. Hg. It may give n-butanol onhydrolysis. Analysis shows 37.7% Sb (theory for diphenyl antimonybutoxide is 34.9% Sb).

As a further illustration of the process for preparing these novelcompounds, 187.0 grams (0.69 mole) of phenyl antimony dichloride may bedissolved in 2 liters of anhydrous benzene and filtered into a -liter,3-neck flask under nitrogen. Ammonia gas may be bubbled into thesolution over a period of 4 hours during which time a white ammoniacomplex precipitates. Anhydrous nbutanol 1920 ml. (1.39 moles plus 50%excess) may be added over a period of 0.5 hour, after which the reactionmass is heated to reflux and refluxed with stirring for 3 hours. Thereaction mass may be cooled and filtered to remove ammonium chloride andsolvent may be stripped from the filtrate to a pot temperature of 100 C.at .2 mm. Hg. The product may have a boiling point of 134l47 C. at 0.3mm. Hg. Analysis shows 35.9% Sb (theory for phenyl antimony dibutoxideis 35.3% Sb).

Thus it will be seen that the novel compositions of this inventionpermit attainment of unexpected results and that these results mayparticularly be obtained by the use of the new compounds R Sb(AR)wherein A may be selected from the group consisting of oxygen, 0, andsulfur, S; n is an integer less than 3; and n is 2 when A is sulfur.

Although this invention has been illustrated by reference to specificexamples, numerous changes and modi fications thereof which clearly fallwithin the scope of the invention will be apparent to those skilled inthe art.

We claim:

1. A novel composition R SbSR' wherein R and R' are independentlyselected from the group consisting of alkyl, alkenyl, alkynyl, aryl,cycloalkyl, and cycloalkenyl.

2. A novel composition as claimed in claim 1 wherein R is aryl.

3. A novel composition as claimed in claim 1 wherein R is alkyl.

4. A novel composition as claimed in claim 1 wherein R is phenyl.

5. A novel composition as claimed in claim 1 wherein R' is alkyl.

6. A novel composition as claimed in claim 5 wherein R is aryl.

7. A novel composition as claimed in claim 5 wherein R is alkyl.

8. A novel composition as claimed in claim 5 wherein R is phenyl.

9. Di-n-butyl antimony lauryl mercaptide.

. Diphenyl antimony dauryl mercaptide.

. Diphenyl antimony n-amyl mercaptide.

. Dibenzyl antimony benzyl mercaptide.

. Dicyclohexyl antimony n-hexyl mercaptide.

. Di-p-chlorophenylantimony n-butyl mercaptide.

15. Diphenyl antimony carboethoxy methyl mercaptide.

16. A novel composition R,,SbX wherein R is selected from the groupconsisting of alkyl, alkenyl, alkynyl, aryl, cycloalkyl, andcycloalkenyl, n is an integer less than 3; and X is alkoxide.

17. A novel composition as claimed in claim 16 wherein R is aryl.

18. A novel composition as claimed in claim 16 Wherein n is 2.

19. A novel composition as claimed in claim 18 wherein R is phenyl.

20. A novel composition R Sb(OR") wherein R is selected from the groupconsisting of alkyl, alkenyl, alkynyl, aryl, cycloalkyl, andcycloalkenyl; n is an integer less than 3; and R" is alkyl.

21. A novel composition as claimed in claim 20 wherein R is aryl.

22. A novel composition as claimed in claim 20 where in n is 2.

23. A novel composition R Sb(OR") wherein R is phenyl; n is an integerless than 3; and R" is alkyl.

24. A novel composition as claimed in claim 23 wherein n is 2.

25. Diphenyl antimony butoxide.

26. Phenyl antimony dibutoxide.

References Cited UNITED STATES PATENTS HELEN M. MCCARTHY, PrimaryExaminer W. F. W. BELLAMY, Assistant Examiner US. Cl. X.R.

